WO2020130086A1 - Inhibiteur de décomposition, film mince, élément d'oscillation laser, et procédé d'inhibition de la décomposition d'un colorant laser - Google Patents

Inhibiteur de décomposition, film mince, élément d'oscillation laser, et procédé d'inhibition de la décomposition d'un colorant laser Download PDF

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WO2020130086A1
WO2020130086A1 PCT/JP2019/049863 JP2019049863W WO2020130086A1 WO 2020130086 A1 WO2020130086 A1 WO 2020130086A1 JP 2019049863 W JP2019049863 W JP 2019049863W WO 2020130086 A1 WO2020130086 A1 WO 2020130086A1
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laser dye
decomposition
decomposition inhibitor
formula
energy level
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PCT/JP2019/049863
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English (en)
Japanese (ja)
Inventor
敏則 松島
誠矢 吉田
工 稲田
有 江崎
利哉 福永
寛之 三重野
望 中村
ファティマ ベンシュイク
マシュー ライアン ライデン
龍太郎 小松
センコウ シン
サンガランゲ ドン アトゥラ サンダナヤカ
安達　千波矢
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国立大学法人九州大学
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/14—Styryl dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
    • H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
    • H01S3/16—Solid materials

Definitions

  • the present invention relates to a decomposition inhibitor capable of suppressing the decomposition of an organic laser dye to emit light for a long time.
  • the present invention also relates to a thin film using such a decomposition inhibitor, a laser oscillator, and a method for suppressing the decomposition of a laser dye.
  • An organic laser dye is an organic compound that causes stimulated emission (amplified spontaneous emission light: ASE) by using light that spontaneously emits as a seed light when transitioning from an excited singlet state to a ground state.
  • ASE amplified spontaneous emission light
  • Laser oscillation using an organic laser dye If the device is realized, flexibility and abundant emission colors can be obtained, and it is expected that it will be highly useful in various fields.
  • As the organic laser dye BSBCz having the following structure is known as a compound exhibiting excellent performance. It has been reported that the BSBCz-doped film has an extremely low ASE oscillation threshold and an extremely high emission quantum yield (see, for example, Non-Patent Documents 1 to 3).
  • the laser oscillation element using BSBCz has a problem that the laser output decreases quickly and the life is short. Therefore, it has been necessary to improve the service life for practical use.
  • the cause of the decrease in the BSBCz laser output has not been clarified yet, and it is hard to say that the measures have been taken sufficiently. Therefore, the present inventors have conducted research to elucidate the cause of the decrease in the laser output of the laser oscillator. Then, by addressing the cause, the investigation was advanced for the purpose of improving the lifetime without deteriorating the light emission characteristics of the laser oscillation element.
  • the present inventors have found that the laser output reduction of the laser oscillation element is caused by the decomposition of the laser dye. On that basis, the conditions capable of suppressing the decomposition of the laser dye were found, and the present invention described below was completed.
  • E S1 (EM) ⁇ E S1 (TR) Formula (1)
  • E Tn (EM) e T1 (TR)
  • E S1 (EM) represents the lowest excited singlet energy level of the laser dye
  • E Tn (EM) represents the excited triplet energy level of the laser dye
  • n is any natural number
  • E S1 (TR) represents the lowest excited singlet energy level of the decomposition inhibitor
  • E T1 (TR) represents the lowest excited triplet energy level of the decomposition inhibitor.
  • E Tn-1 (EM) ⁇ E T1 (TR) Formula (3a) [5] The decomposition inhibitor according to any one of [1] to [3], wherein n is 1. [6] The decomposition inhibitor according to any one of [1] to [4], wherein n is 2. [7] The decomposition inhibitor according to any one of [1] to [6], which has a luminescence lifetime (time until the PL intensity becomes half) of 10 4 seconds or more. [8] A thin film containing an organic laser dye and the decomposition inhibitor according to any one of [1] to [7]. [9] A laser oscillator having the thin film according to [8]. [10] The laser oscillation element according to [9], which is a current excitation type.
  • E S1 (EM) E S1 (EM)> E Tn (EM) Formula (2)
  • E S1 (EM) represents the lowest excited singlet energy level of the laser dye
  • E Tn (EM) represents the excited triplet energy level of the laser dye
  • n is any natural number.
  • E S1 (TR) represents the lowest excited singlet energy level of the decomposition inhibitor
  • E T1 (TR) represents the lowest excited triplet energy level of the decomposition inhibitor.
  • the decomposition inhibitor of the present invention it is possible to suppress the decomposition of the laser dye and allow the laser dye to emit light for a long time.
  • the decomposition inhibitor suppresses the decomposition of the organic laser dye without impairing the light emission from the organic laser dye. Therefore, the reduction of the laser output due to driving can be suppressed, and a long-life laser oscillation element can be realized.
  • FIG. 3 is a schematic diagram showing the chemical structures of BSBCz which is an example of an organic laser dye and Compound 1 which is an example of a decomposition inhibitor of the present invention, and the bond dissociation energy of BSBCz. It is a schematic diagram which shows the structure of the laser oscillation element of this invention. It is a schematic sectional drawing which shows the example of a layer structure of the light emission part which the laser oscillation element of this invention has.
  • FIG. 3 is a graph showing changes with time of (PL intensity/initial PL intensity) of a BSBCz film added with Compound 1, a BSBCz single film, and a Compound 1 single film.
  • FIG. 6 is a graph showing changes with time in (absorption rate/initial absorption rate) of a BSBCz film added with Compound 1, a BSBCz single film, and a Compound 1 single film.
  • 3 is a graph showing changes with time of (ASE strength/initial ASE strength) of a BSBCz film added with Compound 1 and a BSBCz single film.
  • FIG. 3 is a graph showing changes with time of (luminance/initial luminance) of a device 1 using a BSBCz film added with a compound 1 for a light emitting layer and a comparative device 1 using a single film of BSBCz for a light emitting layer.
  • the numerical range represented by “to” means the range including the numerical values before and after “to” as the lower limit value and the upper limit value.
  • the isotopic species of hydrogen atoms present in the molecule of the compound used in the present invention are not particularly limited, and for example, all the hydrogen atoms in the molecule may be 1 H, or some or all of them may be 2 H. (Deuterium D) may be used.
  • the “excitation light” in the present specification is light that causes excitation in a measurement object to generate light emission, and light having a wavelength matching the absorption wavelength of the measurement object is used.
  • E S1 (EM) ⁇ E S1 (TR) Formula (1)
  • E Tn (EM) e T1 (TR)
  • E S1 (EM) represents the lowest excited singlet energy level of the laser dye
  • E Tn (EM) represents the excited triplet energy level of the laser dye
  • n is any natural number.
  • E S1 (TR) represents the lowest excited singlet energy level of the decomposition inhibitor
  • E T1 (TR) represents the lowest excited triplet energy level of the decomposition inhibitor.
  • FIG. 1 shows an example of the energy relationship between the decomposition inhibitor of the present invention and a laser dye
  • FIG. 2 shows the chemical structures of BSBCz as an example of a laser dye and Compound 1 as an example of a decomposition inhibitor.
  • the numerical values in the boxes are the bonds of the bonds indicated by arrows in the ground singlet state S 0 , the lowest excited singlet state S 1 , the lowest excited triplet state T 1, and the excited triplet state T 2 , respectively. Indicates dissociation energy.
  • the laser dye and decomposition inhibitor that can be used in the present invention should not be limitedly interpreted by these specific examples.
  • the lowest excited singlet energy level E S1 (EM) the excited triplet energy level E T2 (EM)
  • the lowest excited level It has a triplet energy level E T1 (EM).
  • the numerical value (eV) attached to the right side of each energy level of the laser dye is the value of the energy level of BSBCz.
  • the decomposition inhibitor of this example is the lowest excited singlet energy level E S1 (TR) having a higher energy level than the lowest excited singlet energy level E S1 (EM) of the laser dye and the lowest excited singlet energy level of the laser dye. It has the lowest excited triplet energy level E T1 (ET) whose energy level is lower than the excited triplet energy level E T1 (EM). That is, this decomposition inhibitor satisfies the formulas (1) to (3) when n is 1.
  • the numerical value (eV) attached to the right of each energy level of the decomposition inhibitor is the value of the energy level of Compound 1.
  • the lowest excited singlet state S 1 when it transits to the lowest excited singlet state S 1 by photoexcitation, it radiatively deactivates to the ground singlet state S 0 as it is, or to the excited triplet state T 2 . It is presumed that after intersystem crossing, internal conversion to the lowest excited triplet state T 1 is carried out. On the other hand, in current excitation, an excited singlet state and an excited triplet state are formed with a probability of 1:3. Of these excited states, the lowest excited singlet state S 1 is radiatively deactivated as it is to the ground singlet state S 0 , or undergoes intersystem crossing and internal conversion to produce the lowest excited triplet state. It is inferred that there is a non-radiative transition from T 1 .
  • the excited triplet state T 2 directly formed by current excitation is internally converted to the lowest excited triplet state T 1 and undergoes no radiation transition.
  • the bond having the smallest bond dissociation energy is the C—N bond (Bond 1, Bond 7) in the lowest excited triplet state T 1 . Therefore, of the excited states of BSBCz, the lowest excited triplet state T 1 is the most unstable, and the decomposition of the C—N bond at the lowest excited triplet state T 1 is a major cause of deterioration of the emission characteristics of BSBCz. It is presumed to be a factor.
  • the lowest excited triplet energy level E T1 (TR) of the decomposition inhibitor is Is lower than the excited triplet energy level E T2 (EM) and the lowest excited triplet energy level E T1 (EM) of the laser dye, the laser dye becomes the excited triplet state T 2 and the lowest excited triplet state T 1 . Then, the excited triplet energy can be eliminated from the laser dye by Dexter transfer to the lowest excited singlet energy level E T1 (TR) of the decomposition inhibitor. Therefore, when the laser dye having the energy relationship shown in FIG.
  • the decomposition inhibitor satisfying the formulas (1) to (3) can effectively suppress the decomposition of the laser dye and cause the laser dye to emit light for a long time.
  • ⁇ E T E Tn (EM) ⁇ E T1 (TR)
  • ⁇ E T preferably satisfies the following formula (4), and more preferably satisfies the following formula (5). .. 2.00 eV> ⁇ E T > 0.00 eV Formula (4) 0.10eV> ⁇ E T> 0.00eV formula (5)
  • the decomposition inhibitor has the lowest excited triplet energy level E T1 (TR) whose energy level is lower than the excited triplet energy level E Tn (EM) of the laser dye. Means to have.
  • ⁇ E T is small, and for example, it can be selected from the range of less than 1.50 eV, less than 1.00 eV, less than 0.50 eV, less than 0.30 eV, less than 0.20 eV, less than 0.10 eV. It is also possible to select from a range of more than 0.01 eV, more than 0.02 eV, and more than 0.03 eV.
  • the formula (3a) is also satisfied.
  • E Tn-1 (EM) ⁇ E T1 (TR) Formula (3a) the excited triplet energy is transferred from the excited triplet state T n (ER) of the laser dye to the lowest excited triplet state E T1 (TR) of the decomposition inhibitor, and unstable from the excited triplet state T n.
  • the internal conversion to the excited triplet state T n-1 is suppressed.
  • the decomposition of the laser dye due to the unstable excited triplet state T n-1 can be effectively suppressed.
  • the decomposition inhibitor has an energy level slightly lower than the excited triplet energy level E T2 (EM) of the laser dye, and the lowest excited triplet energy level E T1 (EM) of the laser dye. It is preferable to have the lowest excited triplet energy level E T1 (TR) having a higher energy level than that.
  • the excited triplet energy level E T2 (EM) of the laser dye easily moves to the lowest excited triplet energy level E T1 (TR) of the decomposition inhibitor, and the excited triplet state T 2 moves to the lowest excited state. Internal conversion to the triplet state T 1 is reliably suppressed. As a result, the decomposition caused by the unstable lowest excited triplet state T 1 of the laser dye can be effectively suppressed.
  • the decomposition inhibitor of the present invention may be used alone or in combination of two or more.
  • a second that satisfies the formulas (1) to (3) when n is 2 A combination of decomposition inhibitors may be mentioned.
  • the description regarding the decomposition inhibitor when n is 2 can be referred to.
  • Preferred as the decomposition inhibitor of the present invention are compounds having a relatively large gap between the lowest excited singlet energy level E S1 (TR) and the lowest excited singlet energy level E T1 (TR).
  • Preferred as such a compound is, for example, an anthracene derivative.
  • Examples of the anthracene derivative include compounds represented by the following general formula (1).
  • R 1 to R 8 each independently represent a hydrogen atom or a substituent
  • R 9 and R 10 each independently represent a substituted or unsubstituted aryl group.
  • R 1 to R 8 may be the same or different from each other
  • R 9 and R 10 may be the same or different from each other.
  • the aryl group for R 9 and R 10 may be a monocycle or a condensed ring in which two or more aromatic rings are condensed, but at least one of R 9 and R 10 is a condensed ring.
  • both R 9 and R 10 may be fused rings.
  • the aromatic ring constituting the aryl group preferably has 6 to 40 carbon atoms, more preferably has 6 to 22 carbon atoms, further preferably has 6 to 18 carbon atoms, and further preferably has 6 to 14 carbon atoms. It is preferably 6 to 10, and particularly preferably.
  • Specific examples of the aryl group include a phenyl group and a naphthalenyl group, a naphthalenyl group is preferable, and a 2-naphthalenyl group is more preferable.
  • Examples of the substituent that R 1 to R 8 may have and the substituent that may be substituted on the aryl group of R 9 and R 10 include an alkyl group, an aryl group, and a silyl group.
  • the silyl group may be an unsubstituted silyl group (—SiH 3 ), or may be one in which at least one of its hydrogen atoms is substituted with an alkyl group or an aryl group.
  • the alkyl group constituting the substituent may be linear, branched or cyclic.
  • the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and further preferably 1 to 6.
  • a methyl group, an ethyl group, an n-propyl group, an isopropyl group and the like can be exemplified.
  • the description and the preferred range of the aryl group constituting the substituent and specific examples thereof the description and the preferred range and specific examples of the aryl group for R 9 and R 10 can be referred to.
  • TTA triplet triplet annihilation
  • decomposition inhibitors used as decomposition inhibitors.
  • the decomposition inhibitor that can be used in the present invention should not be limitedly interpreted by these specific examples.
  • the energy level E T1 (TR) is determined by the following procedure. When phosphorescence is not observed in (2), the calculated value calculated using the density functional theory is used instead.
  • Lowest excited singlet energy level E S1 (EM), E S1 (TR) A compound to be measured is deposited on a Si substrate to prepare a sample, and the fluorescence spectrum of this sample is measured at room temperature (300K). In the fluorescence spectrum, the vertical axis indicates emission and the horizontal axis indicates wavelength.
  • a tangent line is drawn with respect to the fall of the emission spectrum on the short wave side, and a wavelength value ⁇ edge [nm] at the intersection of the tangent line and the horizontal axis is obtained.
  • a value obtained by converting this wavelength value into an energy value by the conversion formula shown below is defined as E S1 (EM) or E S1 (TR) E S1 .
  • Conversion formula: E S1 [eV] 1239.85/ ⁇ edge
  • a spectrometer can be used to measure the emission spectrum.
  • E T1 (EM), E T1 (TR) Lowest excited triplet energy level
  • E T1 (EM) Lowest excited triplet energy level
  • E T1 (TR) The same sample used for the measurement of the lowest excited singlet energy level is cooled to 77 [K]
  • the sample for phosphorescence measurement is irradiated with excitation light, and the phosphorescence intensity is measured using a streak camera.
  • a tangent line is drawn to the rising edge of the phosphorescence spectrum on the short wavelength side, and the wavelength value ⁇ edge [nm] at the intersection of the tangent line and the horizontal axis is obtained.
  • a value obtained by converting the wavelength value into an energy value by the conversion formula shown below is referred to as E T1 (EM) or E T1 (TR).
  • the maximum point having a peak intensity of 10% or less of the maximum peak intensity of the spectrum is not included in the maximum value on the shortest wavelength side described above, and the slope value that is the closest to the maximum value on the shortest wavelength side has the maximum value.
  • the tangent line drawn at the point where the value is taken is the tangent line to the rising on the short wavelength side of the phosphorescence spectrum.
  • the decomposition inhibitor of the present invention preferably has an emission life (time until the PL intensity becomes half) of 10 3 seconds or more.
  • the emission lifetime in a system containing a laser dye and a decomposition inhibitor tends to be limited by the emission lifetime of the decomposition inhibitor.
  • the emission lifetime is preferably 10 4 seconds or more.
  • the “luminescence lifetime” refers to the time until the PL intensity becomes half of the initial PL intensity when the PL (photoluminescence) intensity is measured while photoexciting the sample to be measured with a continuous wave.
  • the description in the column of Test Example 1 can be referred to.
  • the molecular weight of the compound used for the decomposition inhibitor of the present invention or the compound used for the organic laser dye is, for example, 1500 when a thin film containing the organic laser dye and the decomposition inhibitor is intended to be formed by a vapor deposition method and used. It is preferably not more than 1200, more preferably not more than 1200, even more preferably not more than 1000, even more preferably not more than 800.
  • the film containing the organic laser dye and the decomposition inhibitor may be formed by a coating method regardless of their molecular weights. By using the coating method, it is possible to form a film even with a compound having a relatively large molecular weight.
  • a compound containing a plurality of residues in the molecule obtained by removing a hydrogen atom from the compound represented by the general formula (1) is used as a decomposition inhibitor.
  • a polymer obtained by allowing a polymerizable group to exist in the structure represented by the general formula (1) in advance and polymerizing the polymerizable group is used as a decomposition inhibitor.
  • the monomer is polymerized alone or is copolymerized with another monomer, It is conceivable to obtain a polymer having repeating units and use the polymer as a decomposition inhibitor.
  • a compound having a structure represented by the general formula (1) is coupled to each other to obtain a dimer or a trimer and using them as a decomposition inhibitor.
  • Examples of the polymer having a repeating unit containing the structure represented by the general formula (1) include a polymer containing the structure represented by the following general formula (3) or (4).
  • Q represents a group containing the structure represented by the general formula (1)
  • L 1 and L 2 represent a linking group.
  • the carbon number of the linking group is preferably 0 to 20, more preferably 1 to 15, and further preferably 2 to 10.
  • the linking group preferably has a structure represented by —X 11 —L 11 —.
  • X 11 represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom.
  • L 11 represents a linking group, preferably a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group, and a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted More preferably, it is a phenylene group.
  • R 101 , R 102 , R 103 and R 104 each independently represent a substituent.
  • the linking group represented by L 1 and L 2 can be bonded to either Z or R of the structure of the general formula (1) constituting Q. Two or more linking groups may be linked to one Q to form a crosslinked structure or a network structure.
  • repeating unit examples include structures represented by the following formulas (5) to (8).
  • a polymer having a repeating unit containing any of these formulas (5) to (8) is prepared by introducing a hydroxy group into either Z or R of the structure of the general formula (1) and using the compound as a linker to give the following compound: It can be synthesized by reacting to introduce a polymerizable group and polymerizing the polymerizable group.
  • the polymer containing the structure represented by the general formula (1) in the molecule may be a polymer composed of only repeating units having the structure represented by the general formula (1), or may have a structure other than that. It may be a polymer containing the repeating unit having. Further, the repeating unit having a structure represented by the general formula (1) contained in the polymer may be a single type or two or more types. Examples of the repeating unit having no structure represented by the general formula (1) include those derived from a monomer used for ordinary copolymerization. For example, a repeating unit derived from a monomer having an ethylenically unsaturated bond such as ethylene or styrene can be mentioned.
  • the thin film of the present invention is characterized by containing an organic laser dye and the decomposition inhibitor of the present invention.
  • the decomposition inhibitor the description in the above section of “decomposition inhibitor” can be referred to.
  • the “organic laser dye” refers to an organic compound which causes amplified spontaneous emission (ASE) by being supplied with energy.
  • the energy that causes the organic laser dye to emit the spontaneous emission amplified light may be light energy or may be recombination energy generated by recombination of holes and electrons.
  • the organic laser dye is excited to an excited singlet state by irradiation with excitation light, or the organic laser dye is excited to an excited singlet state and an excited triplet state by recombination energy of holes and electrons injected into the thin film. Then, when the excited singlet state transits to the ground state, light is spontaneously emitted, and stimulated emission (radiation of spontaneous emission amplified light) is generated by using the spontaneous emission light as a pilot fire.
  • the decomposition inhibitor contained in the thin film of the present invention may be one kind or a combination of two or more kinds.
  • the description in the above-mentioned "degradation inhibitor" section can be referred to.
  • the organic laser dye any organic compound that emits amplified spontaneous emission light and laser can be used without particular limitation.
  • the following compound (BSBCz) can be mentioned as a preferable example of the organic laser dye combined with the compound 1.
  • the organic laser dye that can be combined with the decomposition inhibitor in the present invention should not be limitedly interpreted by these specific examples.
  • the energy supplied to the thin film is efficiently converted into excited singlet energy and transferred to the organic laser dye, and singlet excitons generated in the organic laser dye are converted.
  • a host material As the host material, an organic compound having the lowest excited singlet energy level higher than that of the organic laser dye can be used. As a result, it becomes possible to easily transfer the excited singlet energy generated in the host material to the organic laser dye and confine the singlet excitons generated in the organic laser dye into the molecule of the organic laser dye. It is possible to bring out the luminous efficiency sufficiently.
  • the decomposition inhibitor may also serve as the host material. However, even if the singlet excitons and the triplet excitons cannot be sufficiently confined, it may be possible to obtain high luminous efficiency. Therefore, if the host material can realize high luminous efficiency, it is particularly limited. Can be used in the present invention without any.
  • the spontaneous emission amplified light and the laser emission originate from the organic laser dye.
  • the emission from the thin film may include at least one of spontaneous emission fluorescence emission, delayed fluorescence emission, and phosphorescence emission in addition to spontaneous emission amplified light and laser. In addition, part or part of the emitted light may be emitted from the decomposition inhibitor or the host material.
  • the content of the decomposition inhibitor in the thin film is preferably 1 to 99% by weight, for example 1 to 50% by weight, 1 to 30% by weight, or 1 to 20% by weight. You may select from within the range.
  • the content of the organic laser dye is preferably 1 to 99% by weight, and may be selected from the range of, for example, 50 to 99% by weight, 70 to 99% by weight, or 80 to 99% by weight.
  • the content of the decomposition inhibitor in the thin film is preferably 0.1 to 50% by weight, more preferably 0.1 to 30% by weight, and 0.1 to 20% by weight. More preferably, it is wt %.
  • the content of the organic laser dye is preferably 0.1 to 20% by weight, more preferably 0.1 to 15% by weight, and further preferably 0.1 to 10% by weight.
  • the host material used for the thin film is preferably an organic compound having a high glass transition temperature. When the thin film is excited by recombination energies of holes and electrons, it is preferable to use, as the host material, one having a hole current transporting ability and an electron transporting ability.
  • the thickness of the thin film can be appropriately selected according to its use. For example, when it is used as a light emitting layer of a laser oscillation element, it is preferably 10 to 1000 nm, more preferably 50 to 1000 nm, More preferably, it is 100 to 1000 nm.
  • the decomposition inhibitor suppresses the decomposition of the organic laser dye without impairing the emission of the organic laser dye, and allows the organic laser dye to emit light for a long time. You can Therefore, by using the thin film of the present invention in the light emitting portion of the laser oscillation element, it is possible to provide a long-life laser oscillation element in which a decrease in laser output due to driving is suppressed.
  • the laser oscillation element has a pair of mirrors 8 and 8 arranged in parallel and a light emitting unit 10 arranged between the pair of mirrors 8 and 8.
  • the pair of mirrors 8 and 8 constitutes a resonator that reflects the light stimulated and emitted from the light emitting unit 10 (spontaneous emission amplified light) to form a standing wave.
  • the light emitting unit 10 has a thin film containing an organic laser dye and the decomposition inhibitor of the present invention, and is configured to emit light amplified by stimulated emission of the organic laser dye to the surroundings.
  • the thin film containing the organic laser dye and the decomposition inhibitor of the present invention may be referred to as a “light emitting layer”.
  • the light emitting unit 10 may be a photoexcitation type light emitting unit that emits spontaneously amplified emission light by supplying light energy, or a current excitation type emission that emits spontaneously amplified emission light by recombination energy of holes and electrons. It may be a department.
  • the photoexcitation type light emitting unit has a structure in which at least a light emitting layer is formed on a substrate. Further, the current excitation type light emitting section has a structure in which at least an anode, a cathode, and an organic layer are formed between the anode and the cathode.
  • the organic layer includes at least a light emitting layer and may be composed of only the light emitting layer or may have one or more organic layers in addition to the light emitting layer. Examples of such other organic layer include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, an exciton blocking layer, and the like.
  • the hole transport layer may be a hole injection transport layer having a hole injection function
  • the electron transport layer may be an electron injection transport layer having an electron injection function.
  • FIG. 4 shows a specific example of the structure of the current excitation type light emitting unit.
  • 1 is a substrate
  • 2 is an anode
  • 3 is a hole injection layer
  • 4 is a hole transport layer
  • 5 is a light emitting layer
  • 6 is an electron transport layer
  • 7 is a cathode.
  • Each member and each layer other than the light emitting layer of the current excitation type light emitting unit will be described below.
  • the description in the section of [Thin film] can be referred to.
  • the description of the substrate and the light emitting layer also applies to the substrate and the light emitting layer of the organic photoluminescence element.
  • the light emitting unit of the present invention is preferably supported by the substrate.
  • the substrate is not particularly limited as long as it is conventionally used for a light emitting element, and for example, a substrate made of glass, transparent plastic, quartz, silicon or the like can be used.
  • anode As the anode in the light emitting portion, a material having a high work function (4 eV or more), an alloy, an electrically conductive compound, or a mixture thereof as an electrode material is preferably used.
  • an electrode material include a conductive transparent material such as metal such as Au, CuI, indium tin oxide (ITO), SnO 2 and ZnO.
  • a material such as IDIXO (In 2 O 3 —ZnO) that can form an amorphous transparent conductive film may be used.
  • the anode may be formed into a thin film by a method such as vapor deposition or sputtering of these electrode materials, and a pattern of a desired shape may be formed by a photolithography method, or if pattern accuracy is not required so much (about 100 ⁇ m or more). ), a pattern may be formed through a mask having a desired shape during vapor deposition or sputtering of the electrode material.
  • a coatable material such as an organic conductive compound
  • a wet film forming method such as a printing method or a coating method can be used.
  • the transmittance is higher than 10%, and the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.
  • cathode a metal having a low work function (4 eV or less) (referred to as an electron injecting metal), an alloy, an electrically conductive compound, or a mixture thereof is used as an electrode material.
  • electrode material include sodium, sodium-potassium alloy, magnesium, lithium, magnesium/copper mixture, magnesium/silver mixture, magnesium/aluminum mixture, magnesium/indium mixture, aluminum/aluminum oxide (Al 2 O 3 ). 3 ) Mixtures, indium, lithium/aluminum mixtures, rare earth metals and the like.
  • a mixture of an electron-injecting metal and a second metal which is a stable metal having a larger work function than that of the electron-injecting metal for example, a magnesium/silver mixture, from the viewpoint of electron injecting property and durability against oxidation and the like.
  • a magnesium/aluminum mixture, a magnesium/indium mixture, an aluminum/aluminum oxide (Al 2 O 3 ) mixture, a lithium/aluminum mixture, aluminum and the like are suitable.
  • the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the sheet resistance of the cathode is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm. Since the emitted light is transmitted, if either the anode or the cathode of the light emitting portion is transparent or semi-transparent, the emission brightness is improved, which is convenient. Further, by using the conductive transparent material mentioned in the description of the anode for the cathode, a transparent or semi-transparent cathode can be produced, and by applying this, an element having both the anode and the cathode having transparency can be formed. It can be made.
  • the injection layer is a layer provided between the electrode and the organic layer for the purpose of lowering the driving voltage and improving the emission brightness, and includes a hole injection layer and an electron injection layer, and between the anode and the light emitting layer or the hole transport layer, And between the cathode and the light emitting layer or the electron transporting layer.
  • the injection layer can be provided if necessary.
  • the blocking layer is a layer capable of blocking diffusion of charges (electrons or holes) and/or excitons existing in the light emitting layer out of the light emitting layer.
  • the electron blocking layer can be disposed between the light emitting layer and the hole transport layer and blocks electrons from passing through the light emitting layer toward the hole transport layer.
  • the hole blocking layer can be disposed between the light emitting layer and the electron transporting layer to prevent holes from passing through the light emitting layer toward the electron transporting layer.
  • the blocking layer can also be used to prevent excitons from diffusing out of the emitting layer. That is, each of the electron blocking layer and the hole blocking layer can also have a function as an exciton blocking layer.
  • the term "electron blocking layer” or "exciton blocking layer” as used herein is used to include a layer having the functions of an electron blocking layer and an exciton blocking layer in one layer.
  • the hole blocking layer has a function of an electron transport layer in a broad sense.
  • the hole blocking layer has a role of blocking the arrival of holes in the electron transporting layer while transporting electrons, thereby improving the recombination probability of electrons and holes in the light emitting layer.
  • the material of the hole blocking layer the material of the electron transport layer described later can be used if necessary.
  • the electron blocking layer has a function of transporting holes in a broad sense.
  • the electron blocking layer has a role of blocking the electrons from reaching the hole transporting layer while transporting the holes, which can improve the probability of recombination of electrons and holes in the light emitting layer. ..
  • the exciton blocking layer is a layer for preventing the excitons generated by the recombination of holes and electrons in the light emitting layer from diffusing into the charge transport layer. It becomes possible to efficiently confine it in the light emitting layer, and the light emitting efficiency of the device can be improved.
  • the exciton blocking layer can be inserted adjacent to the light emitting layer on either the anode side or the cathode side, or both can be inserted simultaneously. That is, when the exciton blocking layer is provided on the anode side, the layer can be inserted between the hole transport layer and the light emitting layer adjacent to the light emitting layer, and when it is inserted on the cathode side, the light emitting layer and the cathode are provided.
  • the layer can be inserted adjacent to the light emitting layer.
  • a hole injection layer or an electron blocking layer can be provided between the anode and the exciton blocking layer adjacent to the anode side of the light emitting layer, and the cathode and the excitation adjacent to the cathode side of the light emitting layer can be provided.
  • An electron injection layer, an electron transport layer, a hole blocking layer, and the like can be provided between the child blocking layer and the child blocking layer.
  • the hole transport layer is made of a hole transport material having a function of transporting holes, and the hole transport layer can be provided as a single layer or a plurality of layers.
  • the hole transport material has any of hole injection or transport and electron barrier properties, and may be an organic substance or an inorganic substance.
  • Examples of known hole transport materials that can be used include triazole derivatives, oxadiazole derivatives, imidazole derivatives, carbazole derivatives, indolocarbazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, Amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline-based copolymers, conductive polymer oligomers, especially thiophene oligomers, etc. It is preferable to use a group tertiary amine compound and a styrylamine compound, and it is more preferable to use an aromatic tertiary amine compound.
  • the electron transport layer is made of a material having a function of transporting electrons, and the electron transport layer can be provided as a single layer or a plurality of layers.
  • the electron transporting material (which may also serve as a hole blocking material) may have a function of transmitting electrons injected from the cathode to the light emitting layer.
  • Examples of the electron transport layer that can be used include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, phenylenylidene methane derivatives, anthraquinodimethane and anthrone derivatives, and oxadiazole derivatives.
  • a thiadiazole derivative in which an oxygen atom of the oxadiazole ring is substituted with a sulfur atom, or a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group can also be used as the electron transport material.
  • a polymer material in which these materials are introduced into the polymer chain or where these materials are used as the polymer main chain can also be used as the electron transport material.
  • the method for forming these layers is not particularly limited, and they may be formed by either a dry process or a wet process.
  • R, R′, and R 1 to R 10 each independently represent a hydrogen atom or a substituent.
  • X represents a carbon atom or a hetero atom forming a ring skeleton
  • n represents an integer of 3 to 5
  • Y represents a substituent
  • m represents an integer of 0 or more.
  • the laser oscillating device of the present invention is configured by arranging the respective mirrors constituting the resonator on both sides of the light emitting unit configured as described above.
  • spontaneous emission amplified light is emitted from the light emitting layer by supplying energy to the light emitting portion, and the amplified light is repeatedly reflected between mirrors and reciprocates to form a standing wave. By extracting this standing wave to the outside, it can be used as laser light.
  • the laser oscillation element of the present invention can be applied to any of a single element, an element having a structure arranged in an array, and a structure having an anode and a cathode arranged in an XY matrix. According to the present invention, by incorporating a decomposition inhibitor in the light emitting layer, it is possible to obtain a laser oscillation element in which the stability of emission is greatly improved.
  • the laser oscillation element of the present invention can be applied to various uses.
  • the emission characteristics are evaluated by a fluorescence lifetime measuring device (Hamamatsu Photonics: Quantaurus-Tau), a fluorescence spectrophotometer (Horiba: FluoroMax-4), an ultraviolet-visible near-infrared spectrophotometer (PerkinElmer). : Lambda 950), an absolute PL quantum yield measuring device (Quantaurus-QY manufactured by Hamamatsu Photonics KK).
  • Table 1 shows the excited singlet energy level and excited triplet energy level of the compounds used in the following test examples. As shown in Table 1, the compound 1 satisfies the formulas (1) to (3) when n is 1 with respect to BSBCz.
  • FIGS. 5 and 6 show time-dependent changes in PL intensity/initial PL intensity when photoexcited with a 365 nm continuous wave
  • FIG. 6 shows time-dependent changes in absorption rate/initial absorption rate when photoexcited with a 365 nm continuous wave. Show.
  • the numerical values in parentheses in FIGS. 5 and 6 indicate the irradiation intensity of continuous waves with which each thin film was irradiated.
  • FIGS. 5 shows time-dependent changes in PL intensity/initial PL intensity when photoexcited with a 365 nm continuous wave
  • FIG. 6 shows time-dependent changes in absorption rate/initial absorption rate when photoexcited with a 365 nm continuous wave. Show.
  • the numerical values in parentheses in FIGS. 5 and 6 indicate the irradiation intensity
  • the BSBCz film to which the compound 1 was added exhibited a lower deterioration rate and higher stability than the BSBCz single film.
  • the half-life of PL intensity of the BSBCz film containing Compound 1 was 3500 seconds, which was 23 times the half-life (150 seconds) of the BSBCz single film. From this, it was found that the addition of Compound 1 significantly improved the stability of the BSBCz film.
  • the stability of the BSBCz film added with Compound 1 is It was suggested to be limited to.
  • the irradiation energy was changed stepwise in the range of 0.205 ⁇ Jcm ⁇ 2 to 113 ⁇ Jcm ⁇ 2 , and a 337 nm pulse wave was emitted to emit light.
  • the spectrum was measured.
  • PL amplification and a decrease in full width at half maximum were observed with an increase in irradiation energy, and emission of spontaneous emission amplified light having a peak wavelength at about 480 nm was confirmed.
  • ASE threshold is about 1.7MyuJcm -2 in BSBCz film added with Compound 1, about 1.6MyuJcm -2 in BSBCz alone film, it was comparable.
  • photoexcitation was performed by irradiating a continuous pulse wave of 337 nm at 400 ⁇ Jcm ⁇ 2 , and ASE intensity/ The change with time of the initial ASE intensity was measured. The result is shown in FIG. 7.
  • 400 ⁇ Jcm ⁇ 2 is an irradiation energy much higher than the ASE threshold of each thin film.
  • the BSBCz film to which the compound 1 was added showed higher stability than the BSBCz single film even under the high excitation condition exceeding the ASE threshold.
  • Example 1 Production and evaluation of organic electroluminescence device using BSBCz film to which compound 1 was added for light emitting layer On a glass substrate on which a cathode made of indium tin oxide (ITO) having a film thickness of 100 nm was formed, Each thin film was laminated at a vacuum degree of 10 ⁇ 4 Pa by a vacuum vapor deposition method. First, Cs and BSBCz were co-evaporated from different vapor deposition sources on ITO to form a layer having a thickness of 60 nm. At this time, the concentration of Cs was set to 20% by weight.
  • ITO indium tin oxide
  • the compound 1 and BSBCz were co-evaporated from different vapor deposition sources and formed to a thickness of 150 nm to form a light emitting layer.
  • the concentration of Compound 1 was set to 10% by weight.
  • molybdenum oxide (MoO x ) was evaporated to a thickness of 10 nm to form a hole injection layer.
  • Ag was vapor-deposited to a thickness of 10 nm, and Al was vapor-deposited thereon to a thickness of 100 nm to form an anode, to obtain an organic electroluminescence element (element 1).
  • FIG. 8 shows changes with time in luminance/initial luminance when each element was continuously driven at a current density of 100 mAcm ⁇ 2 .
  • the device 1 using the compound 1 and BSBCz in the light emitting layer has a lower decrease in luminance than the comparative device 1 not using the compound 1 and exhibits high stability under operation. It was Here, the half-life of luminance was about 125 hours for the element 1 and about 25 hours for the comparison element 1, and the element 1 showed a significantly longer half-life than the comparison element 1.
  • the compounds satisfying the conditions of the formulas (1) to (3) have the effect of improving the stability of the laser dye in the excited state and improving the emission lifetime, and are useful as a laser dye decomposition inhibitor. I found out.
  • the decomposition inhibitor of the present invention can suppress the decomposition of the laser dye and cause the laser dye to emit light for a long time. Therefore, by using the decomposition inhibitor of the present invention, it is possible to provide a long-life laser oscillation element in which a decrease in laser output due to driving is suppressed. Therefore, the present invention has high industrial applicability.

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Abstract

La présente invention concerne un inhibiteur de décomposition pour des colorants laser qui satisfait ES1(EM)<ES1(TR), ES1(EM)>ETn(EM), et ETn(EM)>ET1(TR). ES1(EM) et ETn(EM) sont respectivement le niveau d'énergie d'excitation de singulet minimal et le niveau d'énergie d'excitation de triplet d'un colorant laser ; ES1(TR) et ET1(TR) sont respectivement le niveau d'énergie d'excitation de singulet minimal et le niveau d'énergie d'excitation de triplet minimal de l'inhibiteur de décomposition ; et n est un nombre naturel.
PCT/JP2019/049863 2018-12-20 2019-12-19 Inhibiteur de décomposition, film mince, élément d'oscillation laser, et procédé d'inhibition de la décomposition d'un colorant laser WO2020130086A1 (fr)

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Citations (5)

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Publication number Priority date Publication date Assignee Title
WO2007029718A1 (fr) * 2005-09-06 2007-03-15 Japan Science And Technology Agency Laser à colorant organique à l’état solide
JP2012514862A (ja) * 2009-01-08 2012-06-28 アイメック 固体状有機材料中の三重項励起捕捉
WO2016140164A1 (fr) * 2015-03-02 2016-09-09 国立大学法人九州大学 Éliminateur d'état de triplet, film mince, élément d'oscillation laser et composé
CN108409773A (zh) * 2017-08-09 2018-08-17 北京绿人科技有限责任公司 含三嗪基团的化合物及其应用和一种有机电致发光器件
JP2018177911A (ja) * 2017-04-06 2018-11-15 三星ディスプレイ株式會社Ｓａｍｓｕｎｇ Ｄｉｓｐｌａｙ Ｃｏ．，Ｌｔｄ． 発光材料及びこれを含む有機電界発光素子

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WO2007029718A1 (fr) * 2005-09-06 2007-03-15 Japan Science And Technology Agency Laser à colorant organique à l’état solide
JP2012514862A (ja) * 2009-01-08 2012-06-28 アイメック 固体状有機材料中の三重項励起捕捉
WO2016140164A1 (fr) * 2015-03-02 2016-09-09 国立大学法人九州大学 Éliminateur d'état de triplet, film mince, élément d'oscillation laser et composé
JP2018177911A (ja) * 2017-04-06 2018-11-15 三星ディスプレイ株式會社Ｓａｍｓｕｎｇ Ｄｉｓｐｌａｙ Ｃｏ．，Ｌｔｄ． 発光材料及びこれを含む有機電界発光素子
CN108409773A (zh) * 2017-08-09 2018-08-17 北京绿人科技有限责任公司 含三嗪基团的化合物及其应用和一种有机电致发光器件

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YIFAN ZHANG , STEPHEN R. FORREST: "Existence of continuous-wave threshold for organic semiconductor lasers", PHYSICAL REVIEW B, vol. 84, no. 24, 5 December 2011 (2011-12-05), pages 1 - 4, XP055720756, ISSN: 1098-0121, DOI: 10.1103/PhysRevB.84.241301 *

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